CN105421058B - Surface has polycaprolactone fibroin albumen electrospun fiber membrane of continuous sheet micro nano structure and its preparation method and application - Google Patents
Surface has polycaprolactone fibroin albumen electrospun fiber membrane of continuous sheet micro nano structure and its preparation method and application Download PDFInfo
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- CN105421058B CN105421058B CN201510760843.6A CN201510760843A CN105421058B CN 105421058 B CN105421058 B CN 105421058B CN 201510760843 A CN201510760843 A CN 201510760843A CN 105421058 B CN105421058 B CN 105421058B
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
- D06M14/08—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of synthetic origin
- D06M14/12—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of synthetic origin of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M14/14—Polyesters
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/26—Mixtures of macromolecular compounds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/58—Materials at least partially resorbable by the body
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/04—Macromolecular materials
- A61L31/041—Mixtures of macromolecular compounds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/148—Materials at least partially resorbable by the body
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
- D06M14/02—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin
- D06M14/06—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin of animal origin, e.g. wool or silk
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/12—Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces
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Abstract
There is polycaprolactone fibroin albumen electrospun fiber membrane of continuous sheet micro nano structure and its preparation method and application the invention discloses a kind of surface.The preparation method includes：Fibroin albumen and polycaprolactone are dissolved in hexafluoroisopropanol by step (1), and dissolving is stirred at room temperature, mixed liquor is made；Mixed liquor is carried out electrostatic spinning by step (2), prepares polycaprolactone fibroin albumen blending film；After the vacuum drying of step (3) polycaprolactone fibroin albumen blending film, heating response is carried out under nitrogen protection with PCL monomers, stannous octoate catalyst, polycaprolactone fibroin albumen electrospun fiber membrane is prepared.The polycaprolactone fibroin albumen electrospun fiber membrane that the preparation method is obtained has top layer sheet micro nano structure fiber morphology, specific surface area and fibre diameter are greatly increased, increase possibility of the electrospinning film from hydrophobicity to hydrophilic sex reversal, pulp freeness is substantially increased, space maintains ability, dynamic mechanical and degradation property to increase substantially.
Description
Technical field
There is continuous sheet micro nano structure the invention belongs to technical field of nano material, more particularly to a kind of surface
Polycaprolactone fibroin albumen electrospun fiber membrane and its preparation method and application.
Background technology
After guide tissue regeneration film technology significance is recognized, poly tetrafluoroethylene (ePTFE) is primarily used for drawing
Lead in osteanagenesis research field, but there are a series of complication in use in ePTFE membrane, and need second operation to take out.
And Absorbable membrane controllable degradation speed, taken out without second operation, facilitate patient to operate, reduced patient suffering and shorten healing
Phase, reduce the complication such as film exposure and infection.A large amount of zooperies apply to inducting osseous tissue regeneration (GBR) skill to Absorbable membrane
Art is studied, and mainly includes two classes：1. the polymerization of artificial synthesized lipid polyester, such as PLA (PLA) and PVOH (PGA)
Film.2. animal sources collagem membrane.The two biological characteristics effectiveness of seeking peace also is not quite similar.But existing artificial synthesized lipid polyester
Film, with various shortcomings, such as function time is shorter, and degradation speed is too fast, can not regulate and control, and influences GBR therapeutic effects.
The semicrystalline macromolecular structure of polycaprolactone (PCL), its better heat stability, with more slow degradation rate
With good biocompatibility.PCL catabolites are CO2And H2O, no cytotoxicity, and with good molecule permeability, can
As absorbent medical material.Therefore, it is possible to which polycaprolactone and bioprotein are made into polycaprolactone by electrostatic spinning process
Fibroin albumen blending film.
Although polycaprolactone protein blended spinning film possesses most of advantage of Absorbable membrane, due to the shadow of preparation process
Ring, molecular weight is significantly less than before preparation, so as to cause its mechanical performance and degradation capability poor, as its biomedical applications
Maximum hinders.Therefore, polycaprolactone protein blended spinning film is synthesized and study on the modification has great importance.
The content of the invention
In view of the shortcomings of the prior art, the present invention, which provides a kind of surface, has the gathering in oneself of continuous sheet micro nano structure
Ester fibroin albumen electrospun fiber membrane and its preparation method and application.The preparation method is entered to polycaprolactone fibroin albumen blending film
Row is modified, and forms new sub-micron, nanoscale top layer sheet structural fibers pattern, specific surface area and fibre diameter are greatly increased.
Technical scheme is as follows：A kind of surface has the polycaprolactone fibroin egg of continuous sheet micro nano structure
The preparation method of white appliances spinning fiber film, comprises the following steps：
Fibroin albumen and polycaprolactone are dissolved in hexafluoroisopropanol by step (1), stir molten under room temperature (15~30 DEG C)
Solution, is made mixed liquor；
Mixed liquor is carried out electrostatic spinning by step (2), prepares polycaprolactone fibroin albumen nanometer, sub-micron blending film；
After the vacuum drying of step (3) polycaprolactone fibroin albumen blending film, with polycaprolactone monomers, stannous octoate catalyst
Heating response is carried out under nitrogen protection, and preparing surface has the polycaprolactone fibroin egg of continuous sheet micro nano structure
White appliances spinning fiber film.
The present invention principle be：Polycaprolactone (PCL) has the property for being capable of ring-opening polymerisation, polycaprolactone (PCL) monomer
Ester group and methylene are all there is with polycaprolactone co-polymer structure, the two occurs chain under stannous octoate catalysis and increased, by
Cyclic structure formation chain long molecule, directly determines the mechanics and degradation capability of material, so as to influence the physical property of blending film.
The preparation method of step (1) described fibroin albumen is：Natural silk is put in 0.4wt%~0.8wt% bicarbonates
Boil and taken out after 25~35min in sodium water solution, rinsed repeatedly using deionized water 2~3 times, repeat and boil and rinse 2~3
It is secondary, fibroin albumen is obtained, fibroin albumen is placed in 35~45 DEG C of 40~50h of vacuum drying.
The mass ratio of step (1) fibroin albumen and polycaprolactone is 1：1~3；The degree of polymerization of the polycaprolactone be 600~
800, molecular weight is 70000~90000.
Step (2) electrostatic spinning is carried out under room temperature (15~30 DEG C), and electrospinning parameters are：Spinning distance for 15~
20cm；Spinning voltage is 15~30kV；Flow velocity is 1.0~5.0ml/h.
The mol ratio of step (3) the polycaprolactone fibroin albumen blending film, polycaprolactone monomers and stannous octoate is 900
~1100：900~1100：1.
In step (3) stannous octoate catalystic converter system, temperature is polycaprolactone (PCL) ring-opening polymerisation in influence blending film
One of principal element.
By polycaprolactone fibroin albumen blending film, polycaprolactone monomers and stannous octoate with 2~4 DEG C/min of speed liter
Temperature is to 40~170 DEG C of reactions, and the reaction time is 3~5h, and surface, which is made, by cross-linking modified reaction has continuous sheet micro-nano
The polycaprolactone fibroin albumen electrospun fiber membrane of rice structure.
Preferably, by polycaprolactone fibroin albumen blending film, polycaprolactone monomers and stannous octoate catalyst with 2~4
DEG C/min speed be warming up to 70~100 DEG C of reactions, under preferable temperature, the fibre of polycaprolactone fibroin albumen electrospun fiber membrane
Tie up structure more regular, rule of surface, it is seen that substantial amounts of top layer is sub-micron, micro-nano laminated structure fiber.Original three dimensions
Structure disappears, and a large amount of new space net structures is formed, with preferable specific surface area.In addition, under preferable temperature, yield compared with
Height, can reach more than 70%.
The present invention preparation method is also provided made from surface there is the polycaprolactone of continuous sheet micro nano structure
Fibroin albumen electrospun fiber membrane.
Reaction temperature is 40~170 DEG C, and the surface of preparation has the polycaprolactone fibroin of continuous sheet micro nano structure
Albumen electrospun fiber membrane molecular weight is 2000~9000, and molecular weight is that decision table face has the poly- of continuous sheet micro nano structure
One of caprolactone fibroin albumen electrospun fiber membrane physical property key factor, influences the mechanical performance of high polymer, and the two is in certain
Positive correlation.
In the case where reaction temperature is 70~100 DEG C, surface prepared by the present invention has the poly- of continuous sheet micro nano structure
Caprolactone fibroin albumen electrospun fiber membrane molecular weight is 6000~8000.
The surface has the space dimension of the polycaprolactone fibroin albumen electrospun fiber membrane of continuous sheet micro nano structure
Ability, dynamic mechanical and degradation property is held to increase substantially.
Mechanical test after chemical polymerization is cross-linking modified shows that modified electrospinning film breaking force is raised and carried with reaction temperature
The modification electrospinning film of height, same size and thickness has more eager to do well in everything tensile resistance than unmodified blending film, shows more
Big breaking force, has significant positive role for the mechanical performance for improving Absorbable membrane.
The present invention also provides the polycaprolactone fibroin albumen electrospinning fibre that the surface has continuous sheet micro nano structure
Tie up application of the film in tissue regeneration induction film or tissue engineering bracket is prepared.
The present invention also provides the polycaprolactone fibroin albumen electrospinning fibre that the surface has continuous sheet micro nano structure
Tie up application of the film in battery industry.
The polycaprolactone fibroin albumen electrospun fiber membrane that the present invention is provided has sub-micron, micro-nano top layer laminated structure fine
Pattern is tieed up, specific surface area and fibre diameter are greatly increased, possibility of the increase electrospinning film from hydrophobicity to hydrophilic sex reversal is improved
Fiber surface area, crosslinked modified polycaprolactone fibroin albumen electrospinning film is that a kind of excellent cell adhesion nanometer is new
Section bar material, can be as degradable tissue regeneration induction film, and can be as preparing in the material that other need large specific surface area.
The invention has the advantages that：The present invention is carried out using stannous octoate to polycaprolactone fibroin albumen blending film
Modified, simple to operate, environment friendly and pollution-free, yield is higher.The surface that the present invention is provided has continuous sheet micro nano structure
Polycaprolactone fibroin albumen electrospun fiber membrane has top layer sheet structural fibers pattern, and specific surface area and fibre diameter increase
Plus, possibility of the increase electrospinning film from hydrophobicity to hydrophilic sex reversal improves fiber surface area, space maintains ability, dynamic
Mechanical property and degradation property are increased substantially.
Brief description of the drawings
Fig. 1 is the electronic scanner microscope scanning figure that reaction temperature is 40 DEG C；
Fig. 2 is the electronic scanner microscope scanning figure that reaction temperature is 60 DEG C；
Fig. 3 is the electronic scanner microscope scanning figure that reaction temperature is 80 DEG C；
Fig. 4 is the electronic scanner microscope scanning figure that reaction temperature is 100 DEG C.
Embodiment
With reference to specific embodiment, the present invention will be further described.
The major experimental material and the specification of reagent and manufacturer that embodiment is used are as shown in table 1.
Table 1
Embodiment
Natural silk is put in sodium acid carbonate (0.5wt%) aqueous solution to boil and taken out after 30min by step (1), deionization
Water is rinsed 3 times repeatedly, repeats above step 3 times.Silk after degumming is placed in 40 DEG C of vacuum drying 48h in vacuum drying chamber；
0.3g silks after processing and 0.7g polycaprolactone particles are dissolved in 10ml polyglycolic acid hexafluoroisopropanol solvents, it is even at room temperature
Speed stirring 6 hours, until silk and polycaprolactone are completely dissolved, obtains mixed liquor；
Mixed liquor is placed in 20ml syringes by step (2), drains air, is fixed on double-channel trace syringe pump, if
Speed 2.0ml/h is put, syringe metal needle is connected in high-voltage electrostatic field, electrostatic spinning, electrostatic spinning ginseng are carried out at room temperature
Number is：15~20cm of spinning distance；18~20kV of spinning voltage；Boosting 1.8~2.2ml/h of flow rate pump, at room temperature to mixing
Liquid carries out electrostatic spinning, and the ultra-fine white silk of uniformly continuous can be observed, and continuous electro-spinning 8 hours is collected each group sample with copper mesh, obtained
To polycaprolactone fibroin albumen blending film；
Polycaprolactone fibroin albumen blending film is placed in vacuum drying chamber 40~50 DEG C of dryings 24 hours by step (3), is claimed
Weight is untill weight no longer changes.The more uniform blending film of thickness after 4 parts of drying process is taken in 4 50ml round-bottomed flasks, to divide
Not Jia Ru PCL monomers and stannous octoate catalyst, polycaprolactone fibroin albumen blending film, monomer and stannous octoate mol ratio are
1000：1000：1, after air in flask is taken out to the greatest extent with ability of swimming circulation vacuum pump, nitrogen is filled with into bottle, flask is dipped in and is equipped with
In the thermostatical oil bath cabinet of silicone oil heat, 4 reaction systems respectively with 2~4 DEG C/min of heating rate rise to 40 DEG C, 60 DEG C, 80
DEG C, 100 DEG C reacted.Constant temperature said temperature reacts 4 hours under vacuum nitrogen environmental protection, continues in vacuum nitrogen protection
Room temperature is cooled under environment, obtaining surface has the polycaprolactone fibroin albumen electrospinning fibre of continuous sheet micro nano structure
Film.After reaction terminates, the product prepared under 4 reaction temperatures is taken, electron-microscope scanning, molecular weight detection and mechanics are scanned respectively
Performance detection.Molecular weight detection, mechanics properties testing and yield are as shown in table 2.
Table 2
| Molecular weight | Breaking force (N) | Yield (%) | |
| 40℃ | 2000 | 3.0 | 38 |
| 60℃ | 3200 | 3.7 | 47 |
| 80℃ | 6500 | 5.6 | 70 |
| 100℃ | 7800 | 9.6 | 90 |
(1) ESEM is characterized
Each group sample to be tested is sequentially placed first and is dehydrated 15min in 30%, 50%, 70%, 85%, 90% alcohol,
It is positioned over afterwards in 100% absolute alcohol and is dehydrated 10min, totally 2 times.Metal spraying, FEI-Quanta200 after being dried 24 hours under normal temperature
Type ESEM is characterized to the configuration of surface of each group sample fibres, finds the polycaprolactone fibroin albumen electrospun fiber membrane
Surface has continuous sheet micro nano structure.
40 DEG C of reaction temperature, electronic scanner microscope observation surface has the polycaprolactone of continuous sheet micro nano structure
The fiber morphology of fibroin albumen electrospun fiber membrane, as a result as shown in Figure 1.Some are chaotic for fibre structure, and surface is somewhat irregular, former
There is three-D space structure disappearance.
60 DEG C of reaction temperature, electronic scanner microscope observation surface has the polycaprolactone of continuous sheet micro nano structure
The fiber morphology of fibroin albumen electrospun fiber membrane, as a result as shown in Fig. 2 the polycaprolactone fibroin albumen electrospun fiber membrane surface
With continuous sheet micro nano structure.
80 DEG C of reaction temperature, electronic scanner microscope observes the fiber morphology of polycaprolactone fibroin albumen electrospun fiber membrane,
As a result as shown in figure 3, fibre structure is more regular, rule of surface, it is seen that substantial amounts of top layer sheet structural fibers.Original three dimensions
Structure is disappeared, but a large amount of new space net structures are formed.
100 DEG C of reaction temperature, electronic scanner microscope observation surface have continuous sheet micro nano structure gather oneself in
The fiber morphology of ester fibroin albumen electrospun fiber membrane, as a result as shown in figure 4, fibre structure is somewhat chaotic, original three dimensions knot
Structure is wholly absent.
Molecular weight determination
Each group sample drying and dehydrating processing, with reference to the mean molecule quantity and molecular weight of GB/T 21864-2008 polystyrene
It is distributed examination criteria method and Efficient numerical method method.After being handled through tetrahydrofuran dissolution system, to obtaining sample solution
Rectifying dedusting is carried out, and by 0.2 μm of ultrafiltration membrance filter.Mobile phase solvent after processing is flowed into chromatographic column with constant flow velocity
(flow error<0.01mL/min).Laser light scattering and gel permeation chrommatograph are combined, so as to calculate the molecular weight of sample.
Mechanics Performance Testing
The each group sample to be tested (error is no more than 0.01mm) of thickness close to Bio-Gide films is chosen first, is cut to length
15mm, wide 5mm size thin-films, each group sample is respectively placed on the electronic single-column tester table of SJX-500 types, is pushed away using digital display type
Tensiometer, setting draw speed 10mm/min, 20 DEG C of room temperature, test sample breaking force, breaking force shows that mechanical property is got over
It is good.
Claims (10)
1. a kind of surface has the preparation method of the polycaprolactone fibroin albumen electrospun fiber membrane of continuous sheet micro nano structure,
Characterized in that, the preparation method comprises the following steps：
Fibroin albumen and polycaprolactone are dissolved in hexafluoroisopropanol by step (1), and dissolving is stirred at room temperature, mixed liquor is made；
Mixed liquor is carried out electrostatic spinning by step (2), prepares polycaprolactone fibroin albumen blending film；
After the vacuum drying of step (3) polycaprolactone fibroin albumen blending film, with polycaprolactone monomers, stannous octoate catalyst in nitrogen
Heating response is carried out under gas shielded, preparing surface has the polycaprolactone fibroin albumen electricity of continuous sheet micro nano structure
Spinning fiber film.
2. surface as claimed in claim 1 has the polycaprolactone fibroin albumen electrospinning fibre of continuous sheet micro nano structure
The preparation method of film, it is characterised in that the preparation method of step (1) described fibroin albumen is：Natural silk is put in 0.4wt%
Boil and taken out after 25~35min in~0.8wt% sodium bicarbonate aqueous solutions, rinsed repeatedly using deionized water 2~3 times, then weigh
Boil and rinse 2~3 times again, obtain fibroin albumen, fibroin albumen is placed in 35~45 DEG C of 40~50h of vacuum drying.
3. surface as claimed in claim 1 has the polycaprolactone fibroin albumen electrospinning fibre of continuous sheet micro nano structure
The preparation method of film, it is characterised in that the mass ratio of step (1) fibroin albumen and polycaprolactone is 1：1~3, it is described to gather in oneself
The degree of polymerization of ester is 600~800, and molecular weight is 70000~90000.
4. surface as claimed in claim 1 has the polycaprolactone fibroin albumen electrospinning fibre of continuous sheet micro nano structure
The preparation method of film, it is characterised in that step (2) electrospinning parameters are：Spinning distance is 15~20cm；Spinning voltage is 15
~30kV；Flow velocity is 1.0~5.0ml/h.
5. surface as claimed in claim 1 has the polycaprolactone fibroin albumen electrospinning fibre of continuous sheet micro nano structure
The preparation method of film, it is characterised in that the mol ratio of polycaprolactone fibroin albumen blending film, polycaprolactone monomers and stannous octoate
For 900~1100：900~1100：1.
6. surface as claimed in claim 1 has the polycaprolactone fibroin albumen electrospinning fibre of continuous sheet micro nano structure
The preparation method of film, it is characterised in that step (3) is sub- by polycaprolactone fibroin albumen blending film, polycaprolactone monomers and octanoic acid
Tin is warming up to 40~170 DEG C of reactions with 2~4 DEG C/min of speed, and the reaction time is 3~5h.
7. surface made from a kind of preparation method as described in claim 1 to 6 is any has continuous sheet micro nano structure
Polycaprolactone fibroin albumen electrospun fiber membrane.
8. surface as claimed in claim 7 has the polycaprolactone fibroin albumen electrospinning fibre of continuous sheet micro nano structure
Film, it is characterised in that the surface has the polycaprolactone fibroin albumen electrospun fiber membrane point of continuous sheet micro nano structure
Son amount is 2000~9000.
9. a kind of polycaprolactone fibroin albumen electrospun fiber membrane as claimed in claim 7 is preparing tissue regeneration induction film or group
Application in weaver's engineering support.
10. application of the polycaprolactone fibroin albumen electrospun fiber membrane as claimed in claim 7 in battery industry.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106046135A (en) * | 2016-08-08 | 2016-10-26 | 南通大学 | Silk fibroins with different degradation rates and use thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109629037B (en) * | 2018-12-10 | 2020-04-24 | 武汉大学 | Triazinized silk fibroin modified polycaprolactone nanofiber scaffold and preparation method and application thereof |
| CN111719243B (en) * | 2020-06-09 | 2022-03-01 | 紫罗兰家纺科技股份有限公司 | PGS/SF electrospun membrane and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103341209A (en) * | 2013-07-08 | 2013-10-09 | 苏州大学 | Silk fibroin nanofiber membrane and preparation method thereof |
| CN104313789A (en) * | 2014-03-24 | 2015-01-28 | 长春工业大学 | Method for enhancing mechanical properties of electric spinning membrane |
| CN104874018A (en) * | 2015-06-12 | 2015-09-02 | 李超 | Polycaprolactone-collagen-fibroin nano three-dimensional porous stent and preparation method thereof |
-
2015
- 2015-11-10 CN CN201510760843.6A patent/CN105421058B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103341209A (en) * | 2013-07-08 | 2013-10-09 | 苏州大学 | Silk fibroin nanofiber membrane and preparation method thereof |
| CN104313789A (en) * | 2014-03-24 | 2015-01-28 | 长春工业大学 | Method for enhancing mechanical properties of electric spinning membrane |
| CN104874018A (en) * | 2015-06-12 | 2015-09-02 | 李超 | Polycaprolactone-collagen-fibroin nano three-dimensional porous stent and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Structure Changes of Silk Fibroin ( SF) by Blending with Poly ( ε -caprolactone) PCL) : Characterization of SF and PCL Blended Electrospinning Films;赵荟菁等;《Journal of Donghua University》;20141231;第31卷(第3期);第368-374页 * |
| 不同组分电纺丝素蛋白/聚己内酯超细纤维膜与小鼠成纤维细胞的相容性;谢军军等;《中国组织工程研究与临床康复》;20090716;第13卷(第29期);第5632-5634页 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106046135A (en) * | 2016-08-08 | 2016-10-26 | 南通大学 | Silk fibroins with different degradation rates and use thereof |
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